Stabilization of edible materials



Patented Sept. 28, 1954 STABILIZATION OF EDIB'LE NEATERIALS Joseph A.Chenicek, Bensenville, 111., assignor to- Universal Oil. ProductsCompany, hicago,.lll.,. a corporation of Delaware No Drawing.Application December 30, 1948, Serial No. 68,428

20 Glaims.

This is a continuation-impart of copending application Serial No.692,149, filed August 21, 1946, and now abandoned.

This invention relates to the stabilization of edible materials and moreparticularly to a novel method of preserving the desirable qualitiesthereof.

Edible materials tend to become rancid due to oxidize deterioration.Uusally, it is the oils and fats contained in the edible materials whichundergo undesirable oxidative deterioration but. in some cases the solidportions of the edible materials in close association with the oils andfats also suffer deterioration. Therefore, in accordance with thepresent invention, the novel inhibitor composition may be applied eitherto the solid materials or to the oils which have been separatedtherefrom.

A particular example. of applying the novel inhibitor composition of thepresent invention to a solid material is the treatment of crops in orderto preserve the desirable qualities thereof before and after cutting. Ithas been found that the drying of crops either in: the field or indrying equipment results in a loss of valuable food accessory factors.For example, alfalfa loses anywhere from 45% to 85% of its carotenevalue during the drying treatment. Similarly, carotene is found in sweetpotatoes and in other yellow pigmented plants. Vitaminv B1 (thiaminehydrochloride) is foundin various seeds, grains, nuts, legumes, fruitsand vegetables, while, B2 (riboflavin) isfound in wheat germ and leafyvegetables. Nicotinic acid (niacin) is found in Wheatgerm and inseveralgreen leafy vegetables,

while vitaminBe (pyridoxine). is foundin whole grain cereals, crude,cane. mollasses,v etc. Vitamin.(3 (ascorbic. acid) is found in citrusfruits, tomotoes, greenpeppersand various other fresh fruits andvegetables, and vitaminE is found in wheat germ oil; cotton seedoiLgreenleafy vegetables and. various. grains. Vitamin K1, is. found in.alfalfa, spinach, and. other green vegetables. Pantothenic acidis foundin crude cane molasses and. wheat germ. Several. postulated vitaminswhich. have not as. yet been completely accepted, such. as citrin,gizzard. erosion factor, etc.,. are found. in. various crops, the citrinbeing present imcitrusfoods, and. the gizzard: erosion. factor'beingpresent in.alfafa,.kale, etc. It is understood that the above is merelya brief reference to the content: of various cropsand. that these other.crops. mayalso contain. other vitamins as, for example, spinach-containsvitamins A, B2, later known. as vitamin. G (riboflavin) and C,

2. beets contain vltaminzBr, potatoes contain: vitamin B2,. parsley,cabbage" and. berries contain vitamin- 0,. etc.

In addition to vitamins or in absence of vitamins, various crops containother desirable substances which tend to deteriorate due to oxidativedeterioration. For example, various fatty acids, such as caprylic,capric, lauric, myristic, palmitic, stearic, oleic, linoleic, etc., arefound in the oils of coconut, babassu, palm kernel, olive, castor',peanut, rapeseed, cotton seed,. cornsoya bean, etc. Alcohols are foundin cockfoot grass, wheat, lucerne leaf, etc. Various sterols are foundin plant oils, ergosterol, for example, being found: in soya bean. oil.Further, cropsmay become rancid. and losedesirable qualities such astast, odor, retention of physical shape (nonwilting-l, etc., due tooxidative deterioration.

Thepresent invention offers a-novel method of preventing or retardingtheoxidative. deterioration of these. substances While standing in. thefield, during storage, and. during manufacture.

The-term crops as: used in: the present invention' isintended to;include any substance grown from the soil to be used as a food forhumans or animals, either in. the form as gatheredrfrom the fieldorafter suitable modification in form, such as by pressing, grinding,pulverizing,.slurrying, making intospaste, flour, etc., either' used assuch or after suitable cooking. Thus the present invention is applicableto the treatment. of forage crops, suchas alfalfa, clover, hay, fodder,etc.; grains such as corn, wheat, oats, rice, barley, rye, soy beans,etc..; vegetables such. as carrots,v peas, spinach, beets, potatoes,parsely, cabbage, etc.; fruits including both small fruits, and;thosegrownon trees, such as berries, oranges, lemons, grapefruit,apples, bananas, melons, dates, figs, etc.; nut crops including,peanuts, walnuts, pecans, almonds, chestnuts, hazel nuts, etc; hops,coffee, tea, sugar crops, etc; Also included are crops such as tobacco,which although are not. actually consumed 352 such,, are chewed and theoils therefrom; are-allowed to enter intothe system. It is understood;that the.- above crops-are merely typical representatives and: that thebroad scope of the present invention: is. not: intended to be undulylimited: tovv the crops specifically: mentioned, but istoincludea'lliother crops subject to oxida-- tive deterioration.

Other. solid. edible materials which may bev treated: in thepresentinvention include meat, fish, dairy: products such as cheese,driedmilkand butter, candy, chocolate", etc., and various baked goods.These materials may be treated with the inhibitor either before or aftercooking, baking, smoking or the like.

The edible oils and fats which may be stabilized in accordance with thepresent invention are generally of animal and vegetable origin. Merelyas typical representatives, the following are mentioned; linseed oil,menhaden oil, cod liver oil, castor oil, olive oil, rapeseed oil,coconut oil, palm oil, corn oil, sesame oil, peanut oil, babassu, oil,butter, fat, lard, beef tallow, etc., as Well as hydrogenated oils andfats such as are sold under various trade names including Crisco, Spry,Snowdrift, etc. It is understood that other oils and fats may be treatedwithin the scope of the present invention, including oils and fats whichhave previously been subjected to various treatments, such as blowingwith air, heat treatment, etc.

Many compounds are known which will prevent the development of rancidityin edible oils and fats but practically all of them are unsuitablebecause they are either toxic and therefore cannot be used forstabilizing the edible oils and fats, or else they impart bad odor andtaste to such oils and fats. Some of these compounds are so volatilethey are removed from the oils and fats during cooking or in deep fatdrying, while others are relatively insoluble in oils and fats.

A very important feature of an inhibitor for the stabilization of oilsand fats is that the inhibitor carries over into the bakery products.Many bakery products as, for example, crackers, are kept forconsiderable periods of time in factories, stores or in the homes,before consumption. These bakery goods tend to become rancid due tothese long periods of storage. While some of the known inhibitors arevery potent when used in edible oils and fats, they do not have thisimportant property of carrying over into the bakery goods and thereforeare not completely satisfactory for the purpose intended. It is anobject of the present invention to provide a novel inhibitor compositionwhich will retard deterioration of edible oils and fats and will alsoretard the development of rancidity in the bakery goods.

In one embodiment the present invention relates to a process forstabilizing an edible material which comprises applying thereto aninhibitor composition comprising a 2-alkyl-4- alkoxyphenol and lecithin.

In a specific embodiment the present invention relates to a method ofstabilizing crops subject to oxidative deterioration which comprisesapplying to said crops an inhibitor composition comprising aZ-alkyll-alkoxyphenol and lecithin.

In another specific embodiment the present invention relates to a methodof stabilizing alfalfa which comprises spraying alfalfa with an emulsionof water, a 2-alkyl-4-alkoxyphenol and lecithin.

In another specific embodiment the present invention relates to aprocess for stabilizing edible oils and fats against rancidity whichcomprises incorporating therein a small amount of an inhibitorcomposition comprising a 2-a1kyl-4- alkoxyphenol and lecithin.

In accordance with the present invention, the edible material isstabilized with an inhibitor composition comprising a2-alkyl-4-alkoxyphenol and lecithin. The 2-alkyl-4-alkoxyphenol is avery potent oxidation inhibitor and thus prevents oxidativedeterioration of the edible materials. An important feature of thisinhibitor is that it is non-toxic and, therefore, can be added withoutharmful results. Another important feature of this inhibitor is that ithas the peculiar property of withstanding high temperatures and,therefore, its efiectiveness is not destroyed during subsequent dryingand cooking. Still another important feature of this inhibitor is thatit has the properties of carrying over into the finished cookedproducts, and therefore, it will stabilize the products after cooking.

The lecithin in combination with the 2-allryl-- i-alkoxyphenol serves adual purpose. In one case the lecithin serves both as a solvent and inanother case the lecithin serves both as an emulsifying agent and as asynergist when a water dispersible inhibitor composition is desired.Thus, the mixture of 2-alkylt-alkoxyphenol and lecithin can be used whena Water insoluble composition is desired as in the case of theincorporation of this inhibitor in edible oils. On the other hand, watermay be added to this mixture to form a water dispersable composition,the lecithin serving as an emulsifying agent. In some cases, it isdesired to apply the inhibitor to a water solution or suspension ofedible materials, such as milk, or when it is desired to dip fish orother edible materials into a water solution of inhibitor, etc., and theinhibitor composition for use in such cases should be water dispersible.

It is thus seen that the synergist serves not only as a solvent oremulsifier but also as a synergist. Synergist is the term applied tocertain compounds which, when added to oxidation inhibitors, serve toincrease the effectiveness of the oxidation inhibitor far beyond thatobtained by either the oxidation inhibitor or the added compound whenused alone. As hereinbefore set forth, lecithin has the peculiarproperty or" serving in this dual capacity.

The oxidation inhibitor of the present invention comprises aZ-alkyll-alkoxyphenol of the general structure wherein R and R are alkylgroups.

The alkyl group substituted in the ring may comprise any alkyl groupsuch as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl,tertbutyl, amyl, isoamyl, sec-amyl, tert-amyl, etc. Of these groups thetort-alkyl groups appear to be more effective in contributing to theinhibitor potency of the resultant compound. Likewise, the groups ofhigher molecular weight contribute to other desirable properties of theinhibitor.

The alkyl group of the alkoxy substituent may comprise, for example,methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl,tert-butyl, amyl, isoamyl, sec-amyl, tert-amyl, etc., and may be thesame as or different from the other alkyl substituent group. In general,it may be said that the alkoxy groups of relatively low molecularweight, comprising methoxy or ethoxy groups, appear to have thestrongest influence, although the other groups have considerable value.Particularly preferred oxidation inhibitors comprise2-tert-butyl-4-methoxy phenol and 2-tert-butyll-ethoxy phenol.

The oxidation inhibitor of the present invention may be prepared in anysuitable manner. One particularly convenient method of preparing theinhibitor consists in alkylating a hydroquinone ether and particularly amonalkyl ether with an olefin-acting substance including an olefin,alcohol, ether, etc. For example, hydroquinone monomethyl ether may bereacted. at a temperature of 75 to 80 C". with a tertiary alcoholcorresponding to the group to be substituted; as, for example, tertiarybutyl alcohol, using 85% phosphoric acid as the catalyst. The reactionmixture is stirred continuously until the reaction is complete. Themixture-is then washed with water to remove the remaining acid and isextracted with sodium hydroxide solution to remove the unreactedhydroquinone ether. The insoluble portion is distilled under reducedtemperature and the resulting compound may be further purified byrecrystallization.

The lecithin preferably comprises commercial lecithin which normallycontains cephalin. The lecithin may be obtained from. any source, suchas crude soya bean, corn or cottonseed oil. The lecithin may be used inits crude form or it may be used after refining in the customary manner.

Lecithin as normally available is a waxy solid which upon the additionof suitable acid, such as stearic acid, phosphoric acid, citric acid,ascorbic acid, etc., becomes a liquid. The liquid therefore serves as aliquid solvent for the 2-alkyl-4- alkoxyphenol and thereby may bereadily incorporated into edible materials. Phosphoric acid,

citric acid, and ascorbic acid also function as synergists so that thefinal inhibitor composition is of further high potency.

When the inhibitor is to be used to the treatment of crops, this isreadily accomplished by spraying the inhibitor composition either as asolution or as an emulsion in water over the crops. This method has theadvantage that the amount of inhibitor to be employed may be closelycontrolled in order to obtain even distribution thereof over the crops.It is understood that other methods of applying the inhibitors to cropsmay be employed, such as those in which the inhibitor composition isreleased from a zone of high pressure in the form of a fog or mist.

In some cases better results are obtained when the emulsion and cropsare heated to a temperature of from about 200 to about 500 F. for aperiod of from 10 seconds to 1 hour or thereabouts. However, it isunderstood that, when the inhibitor is applied to crops standing in thefield, it is generally impractical if not impossible to heat themixture. However, when the inhibitor is applied to the crops aftercutting, the heating may be accomplished in driers or by other suitablemeans. Alfalfa, for example, is usually subjected to a drying treatmentand this drying treatment may also serve to effect the desired heatingfor improved results of the emulsion.

The inhibitor may be sprayed on the crops by hand or from airplanes orby any other suitable method in order to distribute the inhibitor evenlyover the crops. The inhibitor will penetrate throughout and within theleaves, seed, etc., of the crops and will thereby serve to preserve thedesirable qualities, not only of the leaves themselves, but also of theoils and the like obtained from the crops. Similarly, the inhibitor willpenetrate into the larger produce such as oranges, lemons, melons,apples, pears, etc., and thereby will serve to preserve the vitamincontent and other desirable properties thereof.

As hereinbefore set forth, a preferred method of applying the inhibitorcomposition to solid edible materials is by spraying. However, it isunderstood that other suitable methods may be employed such as dippingor soakin the edible materials into a solution or emulsion of theinhibitor composition. In some cases a colloid which forms a gel-likestructure may be included in the inhibitor solution or emulsion in orderto form a surface coating for the solid material dipped or soakedtherein. In addition the cut, crops, including fruits, vegetables, etc.,meats and fish, either before or after cooking, baking, smoking, etc.,may be treated in this manner. For example, smoked sausage or othersmoked meats, fillet of fish, smoked fish, etc. which deteriorate instorage may be treated in this, manner.

When the inhibitor composition is to be used in, an, edible oil, it maybe added in any suitable manner. In general, the inhibitor compositionis used in oils and fats in amounts of less than 1% by-weight andgeneraly below 0.01%, based upon the 2-.alkyl-4-alkoxyphenol. In mostinstances the amount thereof will be Within the range of from about0,0001% to about 0.01%. It is understood that the inhibitor compositionof the present invention may also e used in conju t with other oxidationinhibitors, synergists, metal suppressors or other additives to beincorporated in edible materials.

The proportions of lecithin and 2-alkyl-4- alkoxyphenol to be used willvary, depending upon the particular purpose intended and the lecithin to2-alkyl-e-alkoxyphenol ratio on a volume basis may range from about0.05:1 to 300:1 or more. The higher proportions of lecithin are usedwhen the lecithin is to serve as a solvent, and a preferred inhibitorcomposition for this embodiment of the invention comprises 25% by volumeof 2-alkyl-4-alkoxyphenol and 75% by volume of lecithin.

I claim as my invention:

1. A method for stabilizing edible materials which comprisesincorporating therein an inhibitor composition comprising a2-tert-alkyl-4- alkoxyphenol and lecithin.

2. A process for stabilizing crops subjected to oxidative deteriorationwhich comprises applying to said crops an inhibitor compositioncomprising a 2-tert-alkyl-4-alkoxyphenol and lecithin.

3. A process for stabilizing crops subject to oxidative deteriorationwhich comprising spraying said crops with an emulsion of water, anoxidation inhibitor comprising a Z-tert-alkylialkoxyphenol and lecithin.

4. A process for stabilizing alfalfa which comprises spraying thealfalfa with an emulsion of water, 2-tert-butyl-4-alkoxyphenol andlecithin.

5. A process for stabilizing alfalfa to prevent loss in vitamin contentduring drying which comprises spraying the alfalfa with an emulsion ofwater, -2-tert-butyl-4-methoxyphenol and lecithin.

6. A process for stabilizing crops subject to oxidative deteriorationwhich comprises spraying said crops with an emulsion of water, lecithin,and 2-tert-butyl-4-alkoxyphenol.

7'. A process for stabilizing alfalfa to prevent loss in vitamin contentduring drying which comprises spraying the alfalfa With an emulsion ofwater, lecithin, and a 2-tert-alkyl-4-alkoxyphenol.

8. A process for stabilizing edible oils and fats which compriseincorporating therein an inhibitor comprising a2-tert-alkyl-e-alkoxyphenol and lecithin.

9. A process for stabilizing lard which comprises incorporating thereina small amount of 2-tertiary-butyl-4-alkoxypheno1 and lecithin.

10. A process for stabilizing lard which comprises incorporating thereina small amount of 2-tertiary-butyl-4-methoxy phenol and lecithin.

11. A process for stabilizing lard which comprises incorporating thereina small amount of 2-tertiary-butyl-4-ethoxyphenol and lecithin.

12. Edible oils and fats normally tending to become rancid havingincorporated therewith, in an amount sufficient to retard ranciditydevelopment, an inhibitor composition comprising a2-tert-alkyll-alkoxyphenol and lecithin.

13. Edible oils and fats normally tending to become rancid havingincorporated therewith, in an amount sufficient to retard ranciditydevelopment, an inhibitor composition comprising 2-tertiary-butyl-4-methoxy-phenol and lecithin.

14. Edible oils and fats normally tending to become rancid havingincorporated therewith, in an amount sufficient to retard ranciditydevelopment, an inhibitor composition comprising2-tertiary-butyll-ethoxy-phenol and lecithin.

l5. Lard normally tending to become rancid having incorporated therein,in an amount sufiicient to retard rancidity development, an inhibitorcomposition comprising a 2-tert-alkylalkoxyphenol and lecithin.

16. Lard normally tending to become rancid having incorporated therein,in an amount sufficient to retard rancidity development, an inhibitorcomposition comprising Z-tertiary-butyl- 4-methoxy-phenol and lecithin.

17. Lard normally tending to become rancid having incorporated therein,in an amount sufficient to retard rancidity development, an inhibitorcomposition comprising Z-tertiary-butyl- 4-ethoxy-phenol and lecithin.

18. Crops subject to oxidative deterioration containing, in an amountsufiicient to retard said deterioration, an inhibitor compositioncomprising a '2-tert-alkyli-alkoxy-phenol and lecithin.

19. Alfalfa subject to oxidative deterioration containing in an amountsufficient to retard said deterioration, an inhibitor compositioncomprising 2tertiary-buty1-4-methoxy-phenol and lecithin.

20. Alfalfa subject to oxidative deterioration containing, in anamountsufficient to retard said deterioration, an inhibitor compositioncomprising 2-tertiary-butyl-4-ethoxy-phenol and lecithin.

References Cited in the file of this patent UNITED STATES PATENTS BuxtonJune 13, 1950

1. A METHOD FOR STABILIZING EDIBLE MATERIALS WHICH COMPRISESINCORPORATING THEREIN AN INHIBITOR COMPOSITION COMPRISING A2-TERT-ALKYL-4ALKOXYPHENOL AND LECITHIN.